Triazine modified polyphenylene sulfide resins



United States Patent 3,303,170 T RIAZINE MODIFIED POLYPHENYLENE SULFIDE RESINS Roscoe A. Pike, Holden, Mass., assignor to Norton Company, Worcester, Mass, a corporation of Massachusetts No Drawing. Filed Nov. 8, 1963, Ser. No. 322,507 2 Claims. (Cl. 26079) This invention relates to a new organic synthetic resinous polymer having exceptional heat stability, solvent resistance, and oxidation resistance. The resins of my invention are useful as adhesives, sealing compounds, pigments, fillers, rubber compounding materials, molding powders, and binders. These resins can also be flame sprayed, in a reducing or neutral atmosphere to provide protective coatings.

Both linear and crosslinked polyphenylene sulfides containing only carbon aromatic rings have been described in the literature, for example in US. Patents 2,513,188 and 2,538,941 to Macallum. Such resins are made by reacting sulfur with any polyfunctional nuclearly substituted aromatic chloride, bromide or iodide such as phenyl, tolyl, naphthyl, diphenyl, and terphenyl at temperatures from 270 C. to 360 C. for several hours.

The object of the present invention is to provide a modified polyphenylene sulfide resin having more thermal stability than the prior art resins of this type. It is another object to provide a process for making such improved polymers.

It has been found that heterocyclic aromatic units containing nitrogen can be incorporated into polyphenylene sulfide resins to give resins of improved thermal characteristics. Specifically, it has been found that the halophenyltriazine unit can be incorporated into such resin systems resulting in new compositions of matter useful in high temperature applications. The structure of the triazine compounds found useful is as follows:

Where R is hydrogen or a halogen selected from the group consisting of chlorine, bromine, and iodine but at least one R is a chlorine, bromine, or iodine radical. Where only one R is a reactive halogen then the triazine unit can take a position only at the end of polymer chains or branches. Where at least two Rs are reactive the triazine unit will be present at intermediate positions throughout linear or crosslinked polymer molecules. Where all three R groups are reactive then the triazine unit can act as a cross linking center.

The unmodified polyphenylene sulfide resins can be made from nuclear substituted aromatic compounds which contain up to three nuclearly substituted halogen radicals (usually chlorine or bro-mine). Iodine substituted materials are perfectly suitable but such derivatives are less available than the chlorinated and brominated forms. Monosubstituted aromatic compounds may be employed but will act as endblockers so generally such materials would be employed in minor amounts, as would the monofunctional triazine materials, where reasonably high molecular weight resins are desired.

The modified polyphenylene sulfide resins of the present invention may be prepared in the same way as the prior art unmodified resins but with from 1 to 99% of the halogen substituted carbon aromatic compounds replaced by the halogenated phenyl triazine compound. Resins can also be made employing 100% of triazine compound I as the polymerizable monomer. Thus the halogen substituted aromatic compound and the halogenated phenyltriazine materials together with sulfur and an alkaline or alkaline earth oxide or carbonate (preferably sodium carbonate) is heated at 280 to 325 C. for 4 to 6 hours, with a catalyst, or without a catalyst at 300 C. for 20 hours. By this method can be prepared a high molecular weight polymer insoluble in water, methanol, and toluene, having high oxidative thermal stability and a fusion point under atmospheric or molding pressure of from to 350 C: or higher. The catalysts used in the catalyzed reaction include amine polysulfides, copper and nickel containing compounds, basic lead nitrosophenolate, bis- (dialkylthiocarbamyl) sulfides and disulfides, metal sulfides, metals, metal chlorides, ferrocene, and N-halocarboxylamides.

Instead of the metal oxide or carbonate, a metal sulfide can be substituted provided free sulur is still present in at least a significant amount, as taught in Example I of US. Patent 2,538,941. Although I can employ this type of metal sulfide reaction mix when triazine modifiers are employed, with or without catalysts, it is simpler and more economical to employ the metal oxide or carbonate instead of the preformed sulfide. Insofar as the chemistry involved, however, the mixes with the metal sulfide are equivalent to the mixes employing the oxide or carbonate, so long as free sulfur is present in both cases.

The particular portions of monofunctional, difunctional, and trifunctional components in the resins according to my invention are determined by the properties desired. In conformity with the prior art, such as US. Patent 2,513,188, I find that in the production of crosslinked polymers no apparent benefit results from employing more than 25 or 30 mol percent of trifunctional materials, whether the trifunctional group is in the form of a carbon aromatic or the trifunctional phenyl triazine or mixtures of both.

In order to achieve effective and significant upgrading of the thermal properties of the phenylene sulfide polymers, I prefer to employ enough of the phenyl triazine so that at least 10% of the polymer units are triazine units, however as much or as little of the halophenyltriazine may be incorporated into the reaction mix as may be desired. Thus, although the finished resin may include, numerically, from 1 to 100% of triazine nuclei, less than 10% would show only little improvement over the unmodified resin and in view of the relative cost of materials, the use of more than 50% may be uneconomical for some applications. Useful resins have been prepared, however, from 100% triazine type compounds.

An example of a typical resin of this invention, employing a trifunctional triazine is as follows:

Example 1 Into a glass liner which was inserted into a 15 cc. steel pressure Vessel was placed a well-blended mixture of:

p-Dichlorobenzene 2.7 Sulfur 1.1 Na CO 3-5 Tris (p-chlorophenyl) triazine 0.5

The vessel was sealed and heated at 300 C. for 20 hours. After cooling the solid product was granulated and extracted with 250 cc. portions of hot water, methanol, and toluene. The solid polymer was then dried in a vacuum oven at 60 C. for 2 hours. The weight of the dried polymer was 1.98 g.

An example of a resin containing a difunctional tri- B. A similar run was carried out except that 0.14 g. of

azine unit is as follows: N-bromosuccinirnide was added as catalyst and the charge Example H was heated at 300 C. for 5 hours. After extraction as described above there was obtained 2.6 g. of res1n.

Into a glass liner which Was inserted into a 15 Steel Thermal oxidative stability tests were carried out in a Pressure Vessel. Was Placed a charge consisting Ofi forced draft oven to compare the stability of the triazine Grams modified polyphenylene sulfide resins with the stability Di hl b 2,2 of polyphenylene sulfide resins containing no triazine Sulfur 1 units. The resins were prepared as described in Example Di (p-chlorophenyl) phenyl-triazine 0.5 I using the indicated quantities of reactants. The follow Na CO 3.5 ing table summarizes the results:

. 4 moved from the glass liner, followed by extraction with hot water, methanol and toluene. The extracted product was dried in a vacuum oven at 80 to give 2,4 g. of a pea-green colored resin.

TABLE I.HEAT STABILITY OF RESINS OF THIS INVENTION COMPARED TO PRIOR ART Percent Percent Percent Wt. Loss Wt. Loss Wt. Loss Total Wt. Polymer After hrs. After 85-100 After 20 hrs. Loss of Sample at 250 0. hrs. at 300 0. at 400 C.

2 7 (l'hl h 05 124 g.p- 1c oro enzene, g.

triehlorobenzene, 1.1 g. sulfur, 3.5 g. g 2 1;N 21:0)03 (three separate prepara- 5 4 10115 Resin of Example II (two separate prep- 1.1 5.7 6.8 arations). 0. 1 1. 2 4. 6 6. 0 Resin of Example I 0. 0 3.3 5. 3 8.6 Resin of Example IV-A.-- 1.1 8. 4 I 5. 5 15 Resin of Example IV-B-.- 0.9 8. 9 1 6. 8 l6. 6

20 hrs. at 350 C.

Example III Into a 15 cc. steel vessel was inserted a glass liner containing a well-blended mixture of:

Grams Ferr-ocene 0.077 Sulfur 1.1 Na CO 3.5 Tris (p-chlorophenyl) triazine 0.5 p-Dichlorobenzene 2.7

After cooling, the solid product was granulated and extracted with hot Water, methanol, and toluene followed by drying in a vacuum (2 mm.) oven for 2 hours at 60 C.

The resulting product weighed 1.9 grams.

The following illustrates the preparation of a polyphenylenetriazine sulfide resin:

Example IV A. In a glass liner inserted into a 15 cc. steel pressure vessel was charged:

G. Sulfur 1.0 1 Sodium carbonate 3.5 Di (p-chlorophenyl) phenyl triazine 2.7 Tris-(p-chlorophenyl)triazine 0.5

The vessel was sealed and heated at 300 C. for 20 hours. The vessel was then cooled and the product re- In the case of Example IV, analysis for carbon at the end of the heat cycle showed no loss. The initial carbon content was 72.5 wt. percent and was 72.4% at the end of the heating; the theoretical carbon content being 71.8%. The weight loss thus appears essentially due to loss of low molecular wieght fractions and not due to thermal degradation of the resin.

As is apparent from the foregoing, various species of resins may be produced according to this invention. Thus when a monofunctional triazine compound is employed with a difunctional carbon aromatic, such as paradichlorobenzene, the following endblocked structure would result:

[(C6H5)2C3N3C6H4S] s 4 ]n[ s 4 s a( s 5)2] where C N stands for the triazine nucleus and C H and C H are phenyl and phenylene groups, respectively. The value of n would depend upon the degree of polymerization and, for this endblocked polymer, n would have a value betwen 1 and 50. Where It is low, the polymers are useful as high temperature lubricants and heat transfer fluids.

Resins made from reaction mixes employing the di functional triazine unit and a difunctional aromatic compound would consist of linear chains including both triazine units and carbon aromatic units throughout the chains. The empirical formula would be as follows:

. where x can vary from 0.01 to 0.99 and x+y=1. The

' actual polymer chains can be represented as follows:

-ES-BS- TS-BS---TSB-S--Bi I where S represents sulfur and B and T, respectively,

' represent the carbon aromatic units and the triazine units.

When the difunctional triazine compound is employed with a difuncfional aromatic compound at least some tri- -functional carbon aromatic compound, such as a trichloro benzene, the empirical formula would be as follows:

where z varies from 0.01 to 0.30 and x+y+z=1.

The actual structure would be a three dimensional cross linked polymer a small .part of which can he represented as follows:

The actual structure would be represented by a diagrammatic formula similar to the one above for the resin containing the trifunctional carbon aromatic units, but of course with T replacing P and with the linear Ts replaced by Bs.

Other combinations such as the use of both trifunctional triazine units and trifunctional carbon aromatic units with difunctional units, either carbon aromatic or triazine type, can obviously be made but the above examples illustrate the types of combinations contemplated within my invention.

What is claimed is:

1. A method of making a polysulfide polymer comprising reacting together in a sealed container sulfur, a compound selected from the group consisting of alkali metal and alkaline earth metal carbonates, sulfides, and oxides, at least one nuclearly halogen disu bstituted aromatic compound, and a triphenyl triazine in which at least one phenyl group has a nuclearly substituted bromine, chlorine, or iodine, and in which the reactant mixture is heated to from 270 C. to 360 C. for at least 5 hours to complete the reaction.

2. The polymeric reaction product resulting from the method defined in claim 1.

References Cited by the Examiner UNITED STATES PATENTS 2,513,188 6/1950 Macallum 26079.1 2,538,941 1/ 1951 Macallum 26079.1 2,640,047 5/1953 Thurston 26079 3,203,550 8/1965 Schaefer 260-248 DONALD E. CZAIA, Primary Examiner.

LEON I. BERCOVITZ, Examiner.

M. I. MARQUIS, Assistant Examiner. 

1. A METHOD OF MAKING A POLYSULFIDE POLYMER COMPRISING REACTING TOGETHER IN A SEALED CONTAINER SULFUR, A COMPOUND SELECTED FROM THE GROUPCONSISTING OF ALKALI METAL AND ALKALINE EARTH METL CARBONATES, SULFIDES, AND OXIDES, AT LEAST ONE NUCLEARLY HALOGEN DISUBSTITUTED AROMATIC COMPOUND, AND A TRIPHRNYL TRIAZINE IN WHICH AT LEAST ONE PHENYL GROUP HAS A NUCLEARLY SUBSTITUTED BROMINE, CHLORINE, OR IODINE, AND IN WHICH THE REACTANT MIXTURE IS HEATED TO FROM 270%C. TO 360%C. FOR AT LEAST 5 HOURS TO COMPLETE THE REACTION.
 2. THE POLYMERIC RECTION PRODUCT RESULTING FROM THE METHOD DEFINED IN CLAIM
 1. 